CN114269795B - Method for purifying polyalkyl aluminoxane-containing solution using hydroxyl-containing compound and catalyst composition using the same - Google Patents

Method for purifying polyalkyl aluminoxane-containing solution using hydroxyl-containing compound and catalyst composition using the same Download PDF

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CN114269795B
CN114269795B CN202080058203.XA CN202080058203A CN114269795B CN 114269795 B CN114269795 B CN 114269795B CN 202080058203 A CN202080058203 A CN 202080058203A CN 114269795 B CN114269795 B CN 114269795B
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containing solution
catalyst composition
compound
trialkylaluminum
aluminoxane
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CN114269795A (en
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赵允姬
徐宜伶
金乘晓
郑丞桓
金娥琳
韩基元
韩晓晶
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LG Chem Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/602—Component covered by group C08F4/60 with an organo-aluminium compound
    • C08F4/6028—Component covered by group C08F4/60 with an organo-aluminium compound with an alumoxane, i.e. a compound containing an -Al-O-Al-group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/06—Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/07—Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom

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Abstract

The present invention relates to a method for purifying a polyalkylaluminoxane-containing solution using a hydroxyl group-containing compound, a method for producing a catalyst composition using the method, a catalyst composition produced by the production method, and a method for producing an olefin polymer using the catalyst composition.

Description

Method for purifying polyalkyl aluminoxane-containing solution using hydroxyl-containing compound and catalyst composition using the same
Cross Reference to Related Applications
The present application claims the benefit of korean patent application No. 2019-011157 filed in the korean intellectual property office on the date of 9 and 30 of 2019, the disclosure of which is incorporated herein by reference in its entirety.
Technical Field
The present invention relates to a method for purifying a polyalkylaluminoxane-containing solution using a hydroxyl group-containing compound, a method for producing a catalyst composition using the method, a catalyst composition produced by the production method, and a method for producing an olefin polymer using the catalyst composition.
Background
It is well known that polyalkylaluminoxane compositions, which are partial hydrolysates of alkylaluminum, are used as cocatalysts or scavengers for activating procatalysts in the production of olefin polymers. The scavenger is a material added to the catalyst system to react with impurities present in the polymerization reactor, solvent, monomer feed, etc., and is used to prevent catalyst poisoning during polymerization of olefin monomers by reaction with impurities. Specifically, as the scavenger, various compounds such as trialkylaluminum, alkylaluminoxane, dialkylzinc, and dialkylmagnesium are used. As described above, polymethylaluminoxane, polyisobutylaluminoxane, or the like may be exemplified.
Polyalkylaluminoxanes are an example of scavengers that are commercially available as solutions in the state of being dissolved in hydrocarbon solvents such as toluene and can be purchased and used in polymerization reactions when desired. In this case, in addition to the polyalkylaluminoxane as a main component, commercially available polyalkylaluminoxane solutions contain Trimethylamine (TMA), triisobutylaluminum (Tibal), and the like. When it is directly used for polymerization, TMA and Tibal and the like cause a reaction with a transition metal compound as a main catalyst, thereby interfering with the production of an olefin polymer by reducing the catalytic activity of the transition metal compound, or disabling the production of a high molecular weight olefin polymer by participating in the polymerization and acting as a chain transfer agent.
As a typical method for removing impurities such as Tibal from a commercially available polyalkylaluminoxane solution, a method for preventing an additional reaction of Tibal is disclosed, in which a purchased composition solution is reacted with 2, 6-di-t-butyl-4-methylphenol (BHT) to combine BHT with aluminum element of Tibal.
However, although Tibal freely floating in solution can be removed by the above reaction, the product of Tibal binding to BHT is also soluble in the hydrocarbon solvent constituting the polyalkylaluminoxane composition and thus participates in the polymerization reaction. Thus, it is expected that additional problems may occur.
Therefore, there is a need to develop a method of: by maximizing the removal of TiAl present in commercially available polyaluminoxane solutions, the catalytic activity of transition metal compounds during polymerization of olefin monomers is enhanced without interfering with the ability of the polyaluminoxane to scavenge polar impurities or activate the catalyst and permanently remove Tibal from solution, thereby preventing the problem of Tibal from recovering floating in solution due to reverse reactions.
[ Prior art document ]
[ Patent document ]
KR 1996-0005169 B1
Disclosure of Invention
Technical problem
In one aspect of the present invention, a process is provided wherein a solution containing a polyalkylaluminoxane is reacted with a hydroxyl containing compound, the reaction product is filtered and purified, and the filtered and purified product is then mixed with a transition metal compound to prepare a catalyst composition.
Another aspect of the invention provides a catalyst composition using a polyalkyl aluminoxane containing solution containing a small amount of trialkylaluminum.
In yet another aspect, the present invention provides a process for producing an olefin polymer using the catalyst composition.
Technical proposal
According to one aspect of the present invention, there is provided a process for producing a catalyst composition, the process comprising: (S1) preparing a polyalkyl aluminoxane-containing solution comprising polyalkyl aluminoxane, trialkyl aluminum and a hydrocarbon solvent, (S2) reacting the polyalkyl aluminoxane-containing solution with a hydroxyl group-containing compound, (S3) filtering the reaction product of step (S2) and (S4) mixing the filtrate of step (S3) with a transition metal compound.
According to another aspect of the present invention, there is provided a catalyst composition comprising: a polyalkyl aluminoxane-containing solution having polyalkyl aluminoxane, trialkyl aluminum and a hydrocarbon solvent, and a transition metal compound, wherein the trialkyl aluminum is 4.3 mol% or less based on the polyalkyl aluminoxane-containing solution.
According to yet another aspect of the present invention, there is provided a process for producing an olefin polymer, the process comprising polymerizing an olefin monomer in the presence of the catalyst composition.
Advantageous effects
When commercially available solutions containing polyalkylaluminoxanes are purified according to the process of the present invention, trialkylaluminum present in the solution can be removed therefrom. When a polyalkylaluminoxane-containing solution from which trialkylaluminum is removed is used as a catalyst composition, there is an effect of preventing the polymerization reaction from being disturbed by trialkylaluminum and maximizing the activity of a main catalyst compound, thereby efficiently producing an olefin polymer.
In addition, since the insoluble solids produced have been physically removed from the catalyst composition of the present invention, there is no concern about the problem of reverse reaction. In addition, since a separate additive such as BHT is not required, there is an advantage in that only trialkylaluminum is easily removed from the solution and no separate residue remains in the solution, thereby obtaining a high purity olefin polymer.
Detailed Description
Hereinafter, the present invention will be described in more detail to facilitate understanding of the present invention.
It should be understood that words or terms used in the specification and claims of the present invention should not be construed to have meanings defined in commonly used dictionaries. It will be further understood that words or terms should be interpreted to have meanings consistent with their meanings in the context of the relevant art and the technical concept of the present invention, based on the principle that the inventors can properly define the words or terms to best explain the invention.
[ Method of producing catalyst composition ]
The process for producing the catalyst composition of the present invention is characterized by comprising: (S1) preparing a polyalkyl aluminoxane-containing solution comprising polyalkyl aluminoxane, trialkyl aluminum and a hydrocarbon solvent, (S2) reacting the polyalkyl aluminoxane-containing solution with a hydroxyl group-containing compound, (S3) filtering the reaction product of step (S2); and (S4) mixing the filtrate of step (S3) with a transition metal compound.
Step (S1)
Step (S1) is a step of preparing a polyalkylaluminoxane-containing solution containing polyalkylaluminoxane, trialkylaluminum and a hydrocarbon solvent.
The preparation of the polyalkyl aluminoxane containing solution may be entirely included in the present invention regardless of the method or route by which the polyalkyl aluminoxane containing solution is obtained, but in particular, may refer to preparation by obtaining a commercially available polyalkyl aluminoxane containing solution. Currently, commercially available polyalkylaluminoxanes are sold in the form of a solution dissolved in a hydrocarbon solvent and contain a predetermined content of trialkylaluminum, and therefore, there is a problem of degrading the catalytic activity of the main catalyst when participating in polymerization. It is an object of the present invention to perform purification so as to effectively remove trialkylaluminum contained in the polyalkylaluminoxane containing solution prepared in step (S1), and thus, to more effectively use the trialkylaluminum-removed polyalkylaluminoxane containing solution in producing olefin polymers.
Polyalkylaluminoxanes may be added to the catalyst composition to act as a scavenger and/or promoter material.
The polyalkylaluminoxane may be one or more selected from the group consisting of polymethylaluminoxane, polyethylaluminoxane, polyisobutylaluminoxane, and polybutylaluminoxane, and may be, for example, polyisobutylaluminoxane, but is not limited thereto.
The trialkylaluminum may be one or more selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum and methyldiethylaluminum, and may be preferably triisobutylaluminum, but is not limited thereto.
The hydrocarbon solvent may be one or more selected from the group consisting of: an aliphatic hydrocarbon solvent including any one of pentane, hexane, heptane, nonane, decane, cyclohexane and isomers thereof, and an aromatic hydrocarbon solvent including any one of toluene, benzene, xylene and isomers thereof, and the like, and hexane may be preferable, but is not limited thereto.
Preferably, step (S1) may be a step of preparing a mixed solution comprising poly (isobutylaluminoxane), triisobutylaluminum and hexane.
The content of the hydrocarbon solvent contained in the polyalkylaluminoxane-containing solution may be 20 to 99% by weight based on the polyalkylaluminoxane-containing solution. When the content of the hydrocarbon solvent is less than 20% by weight, insoluble solids resulting from the reaction of the polyalkylaluminoxane-containing solution and the hydroxyl group-containing compound are entangled with each other as described below, and thus cannot be sufficiently stirred. Thus, it may be difficult to achieve the effect of the present invention, i.e., to remove trialkylaluminum from a polyalkylaluminoxane-containing solution. Therefore, a sufficient amount of hydrocarbon solvent is required.
Step (S2)
Step (S2) is a step of reacting a solution containing polyalkylaluminoxane with a hydroxyl group-containing compound.
The method of reacting the polyalkyl aluminoxane-containing solution with the hydroxyl group-containing compound may be performed by adding the hydroxyl group-containing compound to the polyalkyl aluminoxane-containing solution prepared in step (S1), for example, by transferring the hydroxyl group-containing compound in a slurry state to the polyalkyl aluminoxane-containing solution. Alternatively, the method may be carried out by adding a solution containing a polyalkylaluminoxane to a hydroxyl group containing compound. The mixing order or rate of the respective materials is not limited as long as the polyalkylaluminoxane-containing solution and the hydroxyl group-containing compound can be brought into contact with each other to react, and can be appropriately adjusted by those skilled in the art.
In step (S2), the trialkylaluminum and the hydroxyl group-containing compound are reacted in a mixed solution of a polyalkylaluminoxane-containing solution and a hydroxyl group-containing compound, thereby producing a solid product, and the solid product may be insoluble in a hydrocarbon solvent in the mixed solution.
Trialkylaluminum is a naturally flammable and water-blocking substance and is therefore classified as a three-stage hazardous substance, unlike trialkylaluminum, the insoluble solid is stable in air and is therefore a non-hazardous substance that does not burn or produce flammable materials. The production process of the present invention not only effectively removes trialkylaluminum but also converts dangerous trialkylaluminum to non-dangerous material and is therefore more preferable than a process of physically separating trialkylaluminum or aluminoxane itself.
In addition, the hydroxyl group-containing compound may be 100 equivalents or less based on 1 equivalent of trialkylaluminum contained in the polyalkylaluminoxane-containing solution. Specifically, the hydroxyl group-containing compound may be 0.01 equivalent to 100.00 equivalents based on 1 equivalent of trialkylaluminum contained in the polyalkylaluminoxane-containing solution, and may be used in an amount of 0.01 equivalent or more, 0.05 equivalent or more, 0.10 equivalent or more, 1.00 equivalent or more, 100.00 equivalent or less, 50.00 equivalent or less, or 10.00 equivalent or less.
When the hydroxyl group-containing compound is less than 0.01 equivalent, the reaction with trialkylaluminum may not be sufficiently achieved, and thus the effect of removing trialkylaluminum may not be significant. When the hydroxyl group-containing compound is more than 100 equivalents, the efficiency of removing trialkylaluminum does not increase in proportion to the amount of the hydroxyl group-containing compound used, and thus economic feasibility may be lowered. In addition, the amount of insoluble solids formed is excessive, so that they are entangled with each other, and it is difficult to stir and filter them.
By hydroxyl-containing compounds is meant compounds containing one or more hydroxyl groups, in particular C2-60 compounds containing two or more hydroxyl groups. Preferably, the hydroxyl-containing compound may be a C2-30 compound containing two or more hydroxyl groups. As described above, the hydroxyl group-containing compound containing two or more hydroxyl groups can react more effectively with trialkylaluminum, and thus can be preferably used.
Materials combined with trialkylaluminum are most likely to cure when the solubility of the hydroxyl-containing compound in organic solvents such as hexane is low. Therefore, the effect of the present invention can be more excellently achieved.
In this case, the hydroxyl group may replace a hydrogen atom on the aromatic ring, or may be coupled to a hydrocarbon chain. When two or more aromatic rings are present, the hydroxyl groups may each replace a hydrogen atom on a different aromatic ring, or may all replace a hydrogen atom on one aromatic ring, but the present invention is not limited thereto.
Specific examples of the hydroxyl group-containing compound may be one or more selected from the group consisting of 1,3, 5-trihydroxybenzene, neopentyl glycol, naphthalene-1, 5-diol, ethylene glycol, bisphenol a, catechol, methylhydroquinone, and 1,2, 3-trihydroxybenzene, but are not limited thereto.
Step (S3)
Step (S3) is a step of filtering the reaction product of step (S2), and is a step of filtering insoluble solids produced by the reaction of trialkylaluminum and hydroxyl group-containing compound in the previous step (S2) using a filter membrane, thereby removing insoluble solids from the mixed solution.
The filtration may be performed using a filter membrane having a pore size of 0.1 μm to 40.0 μm, in particular, a pore size of 0.10 μm or more, 0.15 μm or more, 0.20 μm or more, 1.0 μm or more, 5.0 μm or more, 7.0 μm or more, 40.0 μm or less, 35.0 μm or less, 30.0 μm or less, 20.0 μm or less, 15.0 μm or less, or, for example, 10 μm.
When the pore diameter of the filter membrane is less than 0.1 μm, there may be a problem in that insoluble solids produced by the reaction of trialkylaluminum with hydroxyl-containing compounds may clog the pores of the filter membrane, thereby reducing the filtration efficiency and extending the filtration time. When the pore size of the filter membrane is greater than 40.0. Mu.m, the insoluble solids pass through the filter membrane, resulting in failure to separate and remove the insoluble solids.
In the present invention, a filter membrane having a pore size within a range that allows for efficient removal of the solids produced in step (S2) may be appropriately selected and used. As a result, a high purity polyalkylaluminoxane-containing solution from which trialkylaluminum is effectively removed can be obtained.
In step (S3), the reaction product of step (2) may be immediately filtered, or the reaction product of step (2) may be left to stand to precipitate insoluble solids, and then only the supernatant may be recovered and filtered. Only the supernatant may be recovered and filtered as described above to mainly remove a large amount of insoluble solids, and thus, the efficiency of removing insoluble solids may be improved.
As described above, the method of producing a catalyst composition of the present invention physically removes trialkylaluminum contained in a polyalkylaluminoxane-containing solution through steps (S1) to (S3) so that the trialkylaluminum in the solution can be reduced to 4.3 mol% or less and the content of trialkylaluminum can be further reduced according to reaction conditions, the type of polyalkylaluminoxane and trialkylaluminum, the pore size of a filtration membrane, etc.
Step (S4)
Step (S4) is a step of mixing the filtrate of step (S3) with a transition metal compound.
As described above, in the present invention, a solution in which the relative content of polyalkylaluminoxane is increased and the content of impurities such as trialkylaluminum is reduced is obtained by steps (S1) to (S3). In addition, through the step (S4), the catalyst composition is prepared by mixing a transition metal compound serving as a main catalyst. The catalyst composition prepared as described above comprises polyalkylaluminoxane, which is used as a scavenger and/or a cocatalyst while being free from the interference of trialkylaluminum, and thus the catalytic activity of the transition metal compound can be significantly improved.
[ Catalyst composition ]
The catalyst composition of the present invention comprises: a polyalkyl aluminoxane-containing solution comprising polyalkyl aluminoxane, trialkyl aluminum and a hydrocarbon solvent, and a transition metal compound, wherein the trialkyl aluminum is 4.3 mole% or less based on the polyalkyl aluminoxane-containing solution.
The catalyst composition can be obtained by the production process of the present invention. According to the present invention, the catalyst composition is prepared by removing trialkylaluminum from a polyalkyl-containing aluminoxane solution and mixing the trialkylaluminum-removed polyalkyl-containing aluminoxane solution with a transition metal compound. The trialkylaluminum content contained in the polyalkylaluminoxane-containing solution is as low as 4.3 mole percent or less.
As described above, the catalyst composition comprises a polyalkylaluminoxane and a transition metal compound (procatalyst compound), and may further comprise one or more cocatalyst compounds. At this time, the catalyst composition may refer to a state in which three components of the transition metal compound, the cocatalyst compound, and the polyalkylaluminoxane are mixed simultaneously or in any order to obtain components as a composition having activity.
As the transition metal compound, any compound known to be capable of functioning as a catalyst in the polymerization reaction of olefin monomers can be used.
The cocatalyst may include one or more selected from the following formula 1 or formula 2, but the present invention is not limited thereto.
[ 1]
D(R1)3
In the above formula 1, D is boron, and R 1 are each independently a halogen radical, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms.
[ 2]
[ L-H ] +[Z(A)4]- or [ L ] +[Z(A)4]-
In the above formula 2, L is a neutral or cationic lewis acid, H is a hydrogen atom, Z is a group 13 element, a is each independently an aryl group having 6 to 20 carbon atoms (in which one or more hydrogen atoms may be substituted) or an alkyl group having 1 to 20 carbon atoms (in which one or more hydrogen atoms may be substituted) and a substituent is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.
The compound represented by formula 1 above may include trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, but is not limited thereto.
Examples of the compound represented by the above formula 2 may include trimethylammonium tetraphenyl borate, triethylammonium tetraphenyl borate, tripropylammonium tetraphenyl borate, tributylammonium tetraphenyl borate, trimethylammonium tetrakis (p-tolyl) borate, triethylammonium tetrakis (p-tolyl) borate, tripropylammonium tetrakis (p-tolyl) borate, tributylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o, p-dimethylphenyl) borate, triethylammonium tetrakis (o, p-dimethylphenyl) borate, tripropylammonium tetrakis (o, para-dimethylphenyl) borate, tributylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (p-trifluoromethylphenyl) borate, triethylammonium tetrakis (p-trifluoromethylphenyl) borate, tripropylammonium tetrakis (p-trifluoromethylphenyl) borate, tributylammonium tetrakis (p-trifluoromethylphenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, N-diethylaniline tetraphenyl borate, N-diethylaniline tetrakis (pentafluorophenyl) borate, diethylammonium tetrakis (pentafluorophenyl) borate, trimethylphosphonium tetraphenyl borate, triphenylphosphonium tetraphenyl borate, triphenylcarbonium tetrakis (p-trifluoromethylphenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, trimethylammonium tetraphenyl aluminate, triethylammonium tetraphenyl aluminate, tripropylammonium tetraphenyl aluminate, tributylammonium tetraphenyl aluminate, trimethylammonium tetrakis (p-tolyl) aluminate, triethylammonium tetrakis (p-tolyl) aluminate, tripropylammonium tetrakis (p-tolyl) aluminate, tributylammonium tetrakis (p-tolyl) aluminate, trimethylammonium tetrakis (o, p-dimethylphenyl) aluminate, triethylammonium tetrakis (o, p-dimethylphenyl) aluminate, tripropylammonium tetrakis (o, p-dimethylphenyl) aluminate, tributylammonium tetrakis (p-tolyl) aluminate, trimethylammonium tetrakis (p-trifluoromethylphenyl) aluminate, triethylammonium tetrakis (p-trifluoromethylphenyl) aluminate, tripropylammonium tetrakis (p-trifluoromethylphenyl) aluminate, tributylammonium tetrakis (p-trifluoromethylphenyl) aluminate, trimethylammonium tetrakis (pentafluorophenyl) aluminate, triethylammonium tetrakis (pentafluorophenyl) aluminate, tripropylammonium tetrakis (pentafluorophenyl) aluminate, tributylammonium tetrakis (pentafluorophenyl) aluminate, N-diethylaniline, N-difluoroaniline, and the like, but not limited thereto.
The catalyst composition may be produced by a production method comprising contacting a transition metal compound with a compound represented by the above formula 1 to obtain a mixture, and adding the compound represented by the formula 2 to the mixture.
At this time, the molar ratio of the compound represented by formula 1 to the transition metal compound may be 1:2 to 1:5,000, preferably 1:10 to 1:1,000, and more preferably 1:20 to 1:500.
When the molar ratio of the compound represented by formula 1 to the transition metal compound is less than 1:2, the amount of alkylating agent is very small, and thus there is a problem in that the alkylation of the metal compound is not completely achieved. When it is more than 1:5,000, alkylation of the metal compound is achieved, but there is a problem in that activation of the alkylated metal compound cannot be completely achieved due to side reaction between the remaining excessive alkylating agent and the activator (i.e., the compound represented by the above formula 2).
In addition, the catalyst composition may be produced by a production method comprising contacting a transition metal compound with a compound represented by the above formula 2.
At this time, the molar ratio of the compound represented by formula 2 to the transition metal compound may be 1:1 to 1:25, preferably 1:1 to 1:10, and more preferably 1:1 to 1:5.
When the molar ratio of the compound represented by formula 2 to the transition metal compound is less than 1:1, the amount of the alkylating agent is relatively small, and thus there is a problem in that the alkylation of the metal compound is not completely achieved, thereby decreasing the activity of the catalyst composition. When it is more than 1:25, the activation of the transition metal compound is completely achieved, but there is a problem in that the unit cost of the catalyst composition is uneconomical or the purity of the produced polymer is poor due to the excessive amount of the activator remaining.
When the catalyst composition is produced, a hydrocarbon-based solvent (e.g., pentane, hexane, heptane, etc.) or an aromatic solvent (e.g., benzene, toluene, etc.) may be used as the reaction solvent, but the present invention is not necessarily limited thereto. All solvents useful in the art can be used.
The polyalkyl aluminum content of the polyalkyl aluminoxane containing solution contained in the catalyst composition is relatively low and thus can be used as a scavenger and/or cocatalyst in the production of olefin polymers. Accordingly, the catalyst composition provided in the present invention has excellent activity to promote polymerization reaction, and thus olefin polymers can be produced in good yields using the catalyst composition.
In addition, since the trialkylaluminum is converted to a solid product and filtered, it is permanently removed from the polyalkylaluminoxane containing solution, so that there is no risk of a reverse reaction taking place, so that the trialkylaluminum again appears in the solution. Thus, the stability and predictability of the polymerization reaction can be further improved.
[ Process for producing olefin Polymer ]
The process for producing an olefin polymer of the present invention is characterized by comprising polymerizing an olefin monomer in the presence of a catalyst composition.
The term "polymer" refers to a polymeric compound produced by polymerizing the same or different types of monomers. Thus, the generic term "polymer" includes the term "homopolymer", which is generally used to refer to polymers produced from a single type of monomer, as well as the term "interpolymer", as defined below.
The olefin monomer may be one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene, but is not limited thereto.
In particular, the olefin polymer of the present invention may be an olefin homopolymer, an olefin/α -olefin copolymer, and preferably an ethylene/α -olefin copolymer, depending on the type of olefin-based monomer. In this case, the content of the α -olefin-based monomer (comonomer) may be appropriately selected by those skilled in the art according to the purpose and use of the olefin polymer, and may be about 1 to 99 mol%.
The most preferred polymer production process using the catalyst composition is a solution process. However, when used with an inorganic support (e.g., silica), the catalyst composition may be applied to slurry or gas phase processes.
The catalyst composition may be injected after dissolution or dilution in the following solvents: aliphatic hydrocarbon solvents having 5 to 12 carbon atoms and suitable for use in the polymerization process of olefin monomers (e.g., pentane, hexane, heptane, nonane, decane and isomers thereof), aromatic hydrocarbon solvents (e.g., toluene and benzene), and hydrocarbon solvents substituted with chlorine atoms (e.g., methylene chloride and chlorobenzene). The solvent used herein is preferably used after removing a small amount of water or air (which acts as a catalyst poison) by treatment with a small amount of aluminum alkyl. In addition to the catalyst composition, another cocatalyst may be used.
Examples
Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
[ Preparation of reagents ]
Poly (isobutylaluminoxane) was purchased from Tosho Co., ltd, dissolved in hexane and used. The polyisobutylaluminoxane containing solution purchased from Tosho co., ltd. Contains 4.4 mol% triisobutylaluminum. Hydroxyl containing compounds were purchased from Aldrich co., ltd.
[ Preparation and purification of a solution containing Poly (isobutyl aluminoxane) ]
Production example 1
2.00 Equivalents of 1,3, 5-trihydroxybenzene (based on 1 equivalent of triisobutylaluminum contained in the polyisobutylaluminum-containing solution) were added to a 500mL schlenk bottle, and dried in vacuo for 3 hours. 175g of the polyisobutylaluminoxane containing solution and 175g of hexane were added to another 500mL schlenk flask and prepared.
The 1,3, 5-trihydroxybenzene prepared in the 500mL schlenk flask described above was all transferred as a slurry to the 500mL schlenk flask through a cannula using 30mL hexane, in which a solution containing poly-isobutylaluminoxane and hexane were contained.
After the movement was completed, the mixture was stirred for 12 hours, allowed to stand to form a solid product, and then allowed to stand overnight. When it was left to stand, the supernatant fraction was carefully filtered using a filter having a pore size of 10.0. Mu.m.
Production examples 2 to 11
A solution containing polyisobutylaluminoxane was prepared in the same manner in example 1 except that the modifications shown in the following Table 1 were made.
Comparative production example 1
The polyalkylaluminoxane-containing solution was purchased from Tosho co., ltd. And used as such.
TABLE 1
Hydroxyl group-containing compound Equivalent based on 1 equivalent of triisobutylaluminum Aperture (mum)
Production example 1 1,3, 5-Trihydroxybenzene 2.00 10.00
Production example 2 1,3, 5-Trihydroxybenzene 0.05 10.00
Production example 3 1,3, 5-Trihydroxybenzene 2.00 0.15
Production example 4 1,3, 5-Trihydroxybenzene 3.00 35.00
Production example 5 Neopentyl glycol 4.00 10.00
Production example 6 Naphthalene-1, 5-diol 4.00 10.00
Production example 7 Ethylene glycol 6.60 10.00
Production example 8 Bisphenol-A 4.00 10.00
Production example 9 Catechol (catechol) 2.00 10.00
Production example 10 Methyl hydroquinone 4.00 10.00
Production example 11 1,2, 3-Trihydroxybenzene 2.00 10.00
Comparative production example 1 - - 10.00
Experimental example 1
(1) Triisobutylaluminum (mole%)
The solution obtained by performing the above filtration was dissolved in THF deuteration solvent by 1 H NMR, and the content of the remaining triisobutylaluminum was measured.
(2) Filtration time (hours)
The time until the filter input has all passed through the filter is measured.
(3) Recovery (%)
Recovery (%) = solution containing polyisobutylaluminoxane (g) recovered after filtration/solution containing polyisobutylaluminoxane (g) x100 in reactant state
TABLE 2
Triisobutylaluminum (mole%) Filtration time (hours) Recovery (%)
Production example 1 <0.1 0.1 94
Production example 2 2.900 0.1 95
Production example 3 <0.1 24.0 90
Production example 4 <0.1 0.1 95
Production example 5 <0.1 0.1 90
Production example 6 1.176 0.1 90
Production example 7 0.137 0.1 90
Production example 8 1.470 0.1 90
Production example 9 <0.1 0.1 90
Production example 10 <0.1 0.1 90
Production example 11 0.176 0.1 90
Comparative production example 1 4.400 - -
As shown in table 2 above, in all production examples 1 to 11 prepared by reacting a polyalkylaluminoxane-containing solution with a hydroxyl group-containing compound and then filtering according to the present invention, triisobutylaluminum was largely removed, and thus, it can be seen that the content of remaining triisobutylaluminum was much lower than that of comparative production example 1.
More specifically, in the case of production example 1 (in which 2.00 equivalents of 1,3, 5-trihydroxybenzoic acid was used based on 1.00 equivalents of triisobutylaluminum and a filter membrane having a pore size of 10.0 μm was used), triisobutylaluminum was selectively removed in a short period of time, and thus the filtration time was shortened and the recovery rate was excellent.
Meanwhile, in the case of production example 2 using 0.05 equivalent of 1,3, 5-trihydroxybenzene based on 1.00 equivalent of triisobutylaluminum, the effect of removing triisobutylaluminum based on 1.00 equivalent of triisobutylaluminum is relatively reduced.
In addition, in production example 3 using a filter membrane having a pore size of 0.15 μm, the filtration time was increased; in production example 4 using a filter membrane with a pore size of 35.0 μm, some insoluble solids were observed to be filtered as well.
[ Production of olefin Polymer ]
Example 1
The transition metal compound of the following formula a was prepared using the production method disclosed in korean patent registration No. 10-0738694.
[ A ]
Hexane solvent (900 mL) and 1-octene (300 mL) were charged to a 2L autoclave continuous process reactor, which was then preheated to 150 ℃. Thereafter, ethylene was added to the autoclave continuous process reactor to set the pressure in the reactor to 35 bar, and then 1. Mu. Mol of a transition metal compound, 10 equivalents of dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst, 1.5mmol of the polyisobutylaluminum-containing solution produced in production example 1 were simultaneously added to the reactor. The copolymer was prepared by holding for 8 minutes and continuously conducting the copolymerization reaction. Next, the remaining ethylene gas was removed, and an excessive amount of ethanol was added to the obtained copolymer-containing solution to induce precipitation. The precipitated polymer was washed with ethanol two to three times and then dried in a vacuum oven at 90 ℃ for more than 12 hours to obtain a copolymer.
Example 2
The transition metal compound of the following formula B was prepared using the production method disclosed in korean patent registration No. 10-2016-0019875.
[ B ]
An olefin polymer was produced in the same manner as in example 1, except that the above-mentioned compound of formula B was used as the transition metal compound.
Comparative example 1
An olefin polymer was produced in the same manner as in example 1, except that the polyalkyl aluminoxane containing solution of comparative production example 1 was used in place of the polyalkyl aluminoxane containing solution of production example 1.
Comparative example 2
An olefin polymer was produced in the same manner as in example 2, except that the polyalkyl aluminoxane containing solution of comparative production example 1 was used in place of the polyalkyl aluminoxane containing solution of production example 1.
Table 2 below summarizes the types of transition metal compounds and polyalkylaluminoxane-containing solutions used in examples 1 and 2 and comparative examples 1 and 2.
TABLE 3
Transition metal compound Solutions containing polyalkylaluminoxanes
Example 1 [ A ] Production example 1
Example 2 [ B ] Production example 1
Comparative example 1 [ A ] Comparative production example 1
Comparative example 2 [ B ] Comparative production example 1
[ Analysis of physical Properties of olefin Polymer ]
Experimental example 1
The physical properties of the polymers produced in each of the examples and comparative examples were compared and analyzed. The measurement conditions and methods are as follows, and the measurement results are summarized in table 3 below.
(1) Catalytic Activity (KgPE/mmol)
The catalyst activity is calculated by dividing the resulting polymer by the moles of transition metal compound used in the polymerization reaction.
(2) Melt index (MI 2.16)
Melt index was measured according to ASTM D-1238 (condition E,190 ℃,2.16Kg load).
(3) Density (g/cc)
A sheet having a thickness of 3mm and a radius of 2cm was produced as a sample at 180℃using a press die according to ASTM D-792, and then cooled at a rate of 10℃per minute. The density was measured using a Mettler scale.
(4) Melting temperature (T m, DEG C)
The melting temperature of the polymer was measured using a differential scanning calorimeter (DSC, apparatus name: DSC 2920, manufacturer: TA instrument). Specifically, the polymer was heated to 150℃and then held for 5 minutes. The temperature of the polymer was reduced to-100℃and then again increased. At this time, the temperature rise rate and the temperature decrease rate were adjusted to 10℃per minute, respectively. The melting temperature is determined as the maximum point of the endothermic peak measured during the second temperature increase interval.
(5) Crystallization temperature (T c, DEG C)
The crystallization temperature was determined as the maximum point of the exothermic peak in the curve that appears when the temperature was lowered, using the same method as measuring the melting temperature using DSC.
TABLE 4
As can be seen from the results of table 3 above, in the case of examples 1 and 2 using the catalyst composition produced according to the present invention, the catalyst activity as a whole was significantly increased as compared with the comparative example.
Specifically, when comparing example 1 and comparative example 1 and example 2, which have the same type of transition metal compound, even though the transition metal compound is the same, the catalyst activity of examples 1 and 2, in which triisobutylaluminum was removed, was three times higher than that of comparative examples 1 and 2, respectively, by reacting a solution containing polyisobutylaluminum with a hydroxyl group-containing compound.
As described above, the catalyst composition produced by the production method of the present invention can enhance the catalytic activity of the transition metal compound and effectively produce olefin polymers, which has been confirmed to be an effect that can be achieved in various transition metal compounds, irrespective of the type of transition metal compound.

Claims (11)

1. A process for producing a catalyst composition, the process comprising:
(S1) preparing a polyalkyl aluminoxane containing solution comprising polyalkyl aluminoxane, trialkyl aluminum and a hydrocarbon solvent;
(S2) reacting the polyalkyl aluminoxane containing solution with a hydroxyl group-containing compound and forming a solid insoluble in the hydrocarbon solvent by the reaction of the trialkyl aluminum with the hydroxyl group-containing compound, wherein the hydroxyl group-containing compound is 0.05 equivalent to 100.00 equivalents based on 1 equivalent of trialkyl aluminum contained in the polyalkyl aluminoxane containing solution;
(S3) filtering the reaction product of step (S2) to remove insoluble solids from the solution, wherein the filtering is performed using a filter membrane having a pore size of 0.1 μm to 40.0 μm; and
(S4) mixing the filtrate of the step (S3) with a transition metal compound,
Wherein the hydroxyl-containing compound is a C2-60 compound containing two or more hydroxyl groups.
2. The method of claim 1, wherein the polyalkyl aluminoxane is one or more selected from the group consisting of polymethylaluminoxane, polyethylaluminoxane, and polybutylaluminoxane.
3. The method of claim 1, wherein the polyalkyl aluminoxane is a polyisobutyl aluminoxane.
4. The method of claim 1, wherein the trialkylaluminum is one or more selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tricyclopentylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, and methyldiethylaluminum.
5. The method of claim 1, wherein the trialkylaluminum is one or more selected from the group consisting of triisobutylaluminum, triisopropylaluminum, tri-sec-butylaluminum and triisopentylaluminum.
6. The method of claim 1, wherein the hydrocarbon solvent is 20 wt% to 99 wt% based on the polyalkylaluminoxane containing solution.
7. The method of claim 1, wherein the hydroxyl-containing compound is from 0.05 equivalents to 50.00 equivalents based on 1 equivalent of trialkylaluminum contained in the polyalkylaluminoxane-containing solution.
8. The method of claim 1, wherein the filtering of step (S3) is performed using a filter membrane having a pore size of 0.15 μm to 35.0 μm.
9. The method of claim 1, wherein step (S3) is performed by: allowing the reaction product of step (S2) to stand, and then recovering and filtering the supernatant therefrom.
10. A catalyst composition produced by the method of any one of claims 1 to 9 and comprising:
a polyalkyl aluminoxane containing solution comprising polyalkyl aluminoxane, trialkyl aluminum, and a hydrocarbon solvent; and
A transition metal compound which is a metal compound,
Wherein the trialkylaluminum is 2.9 mole percent or less based on the polyalkylaluminoxane containing solution.
11. A process for producing an olefin polymer, the process comprising polymerizing an olefin monomer in the presence of the catalyst composition of claim 10.
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